A detailed and systematic electron trapping study was conducted in the scientifically important wide bandgap materials LuPO 4 and YPO 4 doubly doped with Ce 3+ and Ln 3+ ͑Ln= Sm, Dy, Ho, Er, Tm͒. By using vacuum-ultraviolet luminescence spectroscopy and detailed thermoluminescence spectroscopy it was possible to establish by two independent methods that the observed electron traps can be assigned to the Ln 3+ codoping ions. It is shown that the associated electron trap depths are determined by the energy separation between the Ln 2+ ground states and the bottom of the conduction band. Both methods reveal a systematic behavior of electron trap depths as a function of the type of Ln 3+ codoping ion that can be explained by recently developed empirical models. Small differences in trap depths obtained by the two methods are discussed in the context of charge-transfer induced relaxation processes and uncertainties in glow peak analysis. Our experiments provide valuable information on 4f n ↔ 4f n , 4f n → 4f n−1 5d, O 2− → Ln 3+ charge transfer and the lowest-energy PO 4 3− group transitions as well as electron trap depths. These transition energies allowed us to construct a complete energy-level diagram for LuPO 4 :Ln 3+/2+ and YPO 4 :Ln 3+/2+ .